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Patented Feb. 20, 1940 UNITED STATES PATENT OFFICE .DIAZOAMINO' ETHER AND METHOD OF I MAKING No Drawing. Application May 14, 1938, Serial No. 207,943

8 Claims.

This invention relates to a new type of diazoamino compounds and to compositions of matter containing them. The diazoamino compounds of the present invention areespecially suitable for I use in the art of dyeing'textile fibers of any origin, forinstance in the dyeing or printing of cellulose, either natural fibers or regenerated cellulose, cellulose esters or ethers,silk, wool, or hair fibers or fabrics. The diazoamino compounds of the present invention are useful as germicides, bactericides, and insecticides.

The diazoamino compounds of the present invention comprise on the one side of the diazoamino group an'aromatic group joined directly to the diazo group, which aromatic group has the property of forming'with an azo coupling component an insoluble azo compound, and on the other side of the diazoamino group a solubilizing group separated from the diazoamino group by an ether group.

Thus the compounds of the invention may be represented by the general formula:

ArN=NI?TRa0 b matic nucleus by an -N=N-N- linkage) of,

' the type ZO M wherein Z represents the radical obtained by subtracting the ,hydroxyl groups from an oxygen acid group, M represents hydrogen or a metal, 0: represents a positive integer designating the number of hydroxy or metaloxy groups joined to the radical Z, for instance 1 or 2, and 1) represents the valence. of Mg. that is, Ar is free. of acid and acid salt groups, such as COOH, SO2OH,, --OSO2OH, OPO(QH)2, AsO(OH)2, and the corresponding groups wherein one or more H is substituted by Na, K, etc.

R3, represents an organic radical joined by a carbon thereof (the same or. a different carbon) to N- and to O-; r

Rb represents an organic radical joined by a carbon thereof (the same or a diiferent carbon) to --O and to -Y;

Re represents hydrogen or an organic radica joined by a carbonthereof to -1I I;

0 represents an ether oxygen; and

Y represents a solubilizing group conferring solubility in water or aqueous alkaline solution.

In the above formula it should be noted that one, two, or more amino-diazo-groups,

, as well as additional aminodiazo groups as indicated above.

Ra and Rb may comprise aliphatic, alicyclic, or aromatic radicals wherein the carbons linked to N--, --O and Y may be separated from one another by O-, CONI-I-a COO,

in any fashion. Re and Rh may be saturated or unsaturated and may contain substituents which do not interrupt the aininic N to I -O to Y linkage,;especially electro-negative substituents, e. g., halogen, or nitro, nitrile, or sulfonic acid ester groups; or CONI-I-, CON=, SOzN'H-, or SO2N= groups attached thereon in any fashion; or radicals conferring solubility in water or alkaline solution,

e. g. sulfite, sulfato, phosphato, sulfonate, carboxylate, or phenolic or alcoholic hydroxyl groups; or additional radicals of the types ArN=.N1|\T--, Ar-N=N- 1 I-R.-o-,

and O-Rb-Y. Ra can also be linked to Rb whereby an inner ether radical is produced. It

should be noted that neither of the carbon atoms joined to O- can be a carbonyl group since in that event the product would be an ester instead of an ether. Certain of the compounds of the ester type are included within the scope of my parent application Serial No. 740,179, filed August 16, 1934, of which thepresent application is in part a continuation.

I may be a radical such as Ra-or Rb. Rc may be linked to, or condensed with, Ra or Rb thus forming a heterocyclic ring in which the aminic nitrogen, or the aminic nitrogen and the ether oxygen, are constituent parts thereof.

In the preferred compounds Ra is a hydrocar bon group which may be further substituted but which does not contain a chain of more than two aliphatic carbon atoms separating the aminic nitrogen from the ether group.

The resistance of the more stable diazoamino compounds to hydrolysis may be reduced by the introduction of electro-negative substituents attached to the carbon joined to the diazoamino nitrogen or attached-to a carbon adjacent to this carbon. Electro-negative groups suitable for accomplishing this purpose have been set forth above in the definition of Ra and Rb.

. The diazoamino compounds of this invention, especially those that contain a plurality of hydroxyl groups and/or carboxylic acid radicals, COOMe, and/or sulfonic acid radicalsSOaMe, wherein Me represents hydrogen, sodium or potassium,'possess notable solubility in water or aqueous alkaline solutions and hence are especially valuable for use where rapid solution is desirable. This property constitutes a marked advantage of the compounds of the present invention whether they are employed as dyestuffs, or insecticides, bactericides, etc. I The diazoamino compounds of the present in vention may be prepared by coupling an aromatic diazonium salt of the general formula Ar-(N=Nz)x 2 (wherein Ar represents an aromatic radical as previously set forth; 2 represents'an acid group, for example Cl; and a: represents a positive integer indicating the number of diazo-substituents on the aromatic residue, preferably 1, 2, or 3) with the stoichiometrical quantity of a primary or secondary amino-ether of the general formula:

HNR.O Rb -Y wherein Ra, Rb, and Re have the values previously ascribed. However they should not be such as will couple with the diazo group to form an azo compound. I, i I, e

The reaction to form the diazoamino compounds proceeds at low temperatures. The

coupling of the diazonium salt with the aminoether'is advantageously effected by bringing to gether-aqueou's solutions of the individual reactants in the presence of an alkaline medium which serves to bind the acid liberated by the coupling. The diazoamino compound may be recovered 'by crystallization, including salting out, or by drying the solution containing it in in the presence of coupling components and hence may be used for the preparation of stable dye compositions comprising one or more of the "diazoamino compounds and a suitable coupling component or components.

Coupling of the diazoamino compounds of this invention with coupling components which are normally employed with the diazo compounds corresponding to the said diazoamino compounds may be effected by treatment with acid, as by introducing an acid into the bath containing a solution of the diazoamino compound and the coupling component, or by subjecting fibers containing a coupling component to the action of an acidified bath of the diazoamino compound or by subjecting fibers impregnated with a solution or paste of the diazoamino compound and a coupling component to the action of an acid bath or acid vapors.

The proportions of coupling component to diazoamino compound in the compositions of my invention may vary widely. Preferably, however, I mix the two constituents in about stoichiometrical quantities. The compositions may comprise the constituents in dry form or insolution. The dry composition may be prepared by mechanical admixture of the two constituents in solid phase or by evaporating a solution of the two constituents. i

The compositions containing a diazoamino compound of the present invention and a coupling component may be applied to textile fibers in the usual manner. They are particularly suitable for the dyeing of fabrics by the printing process. g

A printing paste is prepared by mixing together about stoichiometrical quantities of a diazoamino compound of the type previously defined and a coupling component, adding to the mixture sodium hydroxide solution in quantity sufficient to dissolve the components, and making up the mixture to a printing paste in the usual manner by adding thereto a thickening agent such as starch or gum tragacanth and the necessary quantity of water. If desired, Turkeyred oil or other assistants or solvents may be added. The fabric is printed with this printing paste in the usual manner; then either with or without drying and steaming, it is treated for a short time, say around twenty seconds, in a bath containing an acid, for example per cent to 5.0 per cent of formic acid, acetic acid, or oxalic acid at a temperature between and 95 C. The bath may also contain other assistants, penetrants, etcbfor example'around 5 per cent ofGlauber's salt (Na2SO4JOI-I2O) ,or sodium chloride (NaCl), or sodium acetate ((H-IsCOONa). Instead of, developing the dye in an acid bath, it may be developed by passing it through an acid-vapor ager containing, for example, steam and vapors of acetic orformic acid or both. After development of the print in any of the above manners, it may be rinsed, washed, and dried in the customary manner.

The following examples of amines which may be diazotized and coupled to form diazoamino compounds within the purview of the present 2ethylamino-4-chlor-phenoxy-butyl sulluric acid S :11 I n-seonn-oQ n OH:

COOH 1-methylaminoethoxy-ii-sulfonyl-fi-benzoic acid H N G2H4 O"- O-,CH-C 0 OH CHr-C O O H 2methylaminoethoxy phenoxysuccinic acid CH3 1H3 (Lon-coon 0 H: C 0 0H N-methyl-N-methylamino-ethyl-ortho-amino-phenoxysuccinic acid u-i-r-ozm-o-olnisoan 47) Ha M I Methylaminoethory-ethyl-sulionic acid 3-(3'-amino-2-hydroxy-propyloxy)-2-hydroxy-propyl sulfate onnEHn-Q o-om-oownpmonomi-omonj Ethylene-di-(amino-pphenoxy-acetyl-glucamine) The illustrative amino ethers containing acidic groups have been set forth above in terms of the free acids or. phenols. Normally it is advantageous to employ these compounds in the form of soluble salts; hence they may be employed in the forms wherein the hydrogens of the acid or phenolic groups are substituted by metals, e. g., sodium or potassium.

Any of the coupling components in use for coupling with diazo compounds may be employed with the diazoamino compounds of the present invention, for instance, the naphthols and naphtholates, 2,3-hydroxynaphthoic acid, 2,3-hydroxynaphthoic acid arylides, 2,6-hydroxynaphthoic acid arylides, alkyl-phenyl-pyrazolones, aceto-acetic acid arylides, 2-hydroxy-carbazoleortho-carbonic arylides, and the 2,4-dihydroxyquinolines. Specific examples of these coupling components are given in connection with the following examples and in the tableof dyestuff compositions which is a part hereof. l

The following examples will serve to further illustrate the present invention (parts are by weight) EXAMPLE 1 Part A 142 parts 1-methyl-4=-chlor-2-aminobenzene sarestirred with 250 parts aqueous hydrochloric acid of 19 Be. (about 30% I-ICl) and ice is added to keep the temperature between 0 and. 5 C. 69 parts sodium nitrite (100% NaNO2) are dissolved. in 200 parts water and this solution is addedto the cooled amine hydrochloride. After diazotization is complete, the diazo solution is filtered and 429 parts of l-methylaminobenzene-2A-d1- (oxyethyl-sodium sulfate) (amine #7) added,

followed by an addition of sodium carbonate, while stirring, until the liquid reacts alkaline to Brilliant Yellow indicator paper. Coupling occurs gradually with progressive disappearance of the diazo body, and after two hours standing,

a test made with a solution of R salt remains negative. Enough sodium chloride is then added to render the solution saturated, whereupon the light yellow diazoamino compound separates. It is filtered oif, pressed, and dried, preferably in vacuum at 50 C.

The diazoamino compound has the following probable formula:

The 1-methylaminobenzene-2,4=-di(oxy-ethyl-sulfate) is very conveniently prepared from methylamino-di(hydroxy-ethoxy) benzene by sulfation.

Part B A dyestufi' composition is made by mixing and grinding 582 parts of the diazoamino compound as obtained according to part A above with 300 parts of the sodium salt of 2,3hydroxy-naphthoic acid-ortho-toluidide. A printing paste is then prepared by dissolvingGO parts of the dyestuii composition in '60 parts Cellosolve (monomethyl ether of ethylene glycolland 330 parts hot water. The solution is thickened with 550 parts of a starch tragacanth thickener. Cotton material is printed with this paste by means of an engraved copper roll. The printed material is dried and the insoluble azo dye developed by a passage during to seconds in a hot solution (210 F.) of 5% Glauber salt, 5% acetic acid and 2% formic acid. The printed pattern is thus developed in a brilliant red dyeing due to formation of the red azo dye of the following probable constitution:

composition which, when applied under conditionsas describedabove yields a yellow print due to formation, upon acidic aftertreatment cf the textile fabric, of the yellow dyestuif of the following probable constitution:

. .CH: v

' l EH: 1 I -CH0OOH EXAMPLE 2 PdrtA 127.5 parts of 3-chloro-1-aminobenzene are stirred with 250 parts hydrochloric acid 19 B. The crystal slurry is then cooled to 0 to 5 C., by the addition of ice and diazotized with a solution of 69 parts sodium nitrite (100%) in 300 parts of cold water. When diazotization is completed 289 parts of methylamino-benzyl-4-oxyethane sodium sulfonate famine #10) are added while agitating, followed by suflicient sodium carbonate solutionto render the liquor slightly alkaline. Coupling occurs very readily, whereupon sodium chloride is added, resulting in the precipitation of the corresponding diazoamino compound.

The product is filtered ofi", washed with a saturated sodium chloride solution, pressed free of the brine solution and dried at 60 C., in vacuum.

It is lightly colored, readily soluble in Water, very stable towards alkaline hydrolysis, but regenerates the 3-chlor-1-aminobenzene diazonium chloride upon acid hydrolysis. Its probable formula is the following:

I 7 (k z v 01 Part B Equimolecular amounts of the above dry di-. azoamino compound and of the sodium salt of 2,3-hydroxynaphthoic acid anilide are intimately mixed and ground together. A dyestuff composition is thus obtained which is appliedin a manner similar to that described in Example 1. The use of the composition maybe described by the pad dyeing of cellulose for which it is very suitable. i

parts of above dry mixture are dissolved in 80 parts alcohol followed by the addition of 300 parts hot water. The solution is then diluted to 1000 parts total weight with water at 40 C., containing 1 per cent of a 6 per cent gum tragacanth solution. The rayon fabric composed of regenerated cellulose is passed through this solution, which is at a temperature'of approximately 45 C., in a padding machine so regulated as to leave per cent of the dye liquor on the padded material, based on the Weight of the-fabric. Thereafter the fabric is very rapidly dried over hot cans and directly passedthrough a continuous steamer supplied with saturated steam containing 4 per heated acid-proof plate, whereby instantaneous vaporization and mixing with the main steam supply takes place.

Thus, a very brilliant plain shade of orange is obtained possessing excellent fastness properties, due to formation of the orange dyestuff of the probable formula:

In the above example the methylamino-benzyl- 4-oxy-etha'ne-sodium sulfonate may be replaced by an equimolecular amount of l-methylamino-v benzene-2,4-di(oxy sodium acetate) or by an equimoleoular amount of l-ethylamino benzene- 4-oxy benzyl-2,5-disulfonic acid (with corresponding results).

EXAMPLE 3 Part A stirring, followed by a slow and careful addition of caustic soda 20% solution until the reaction mixture is alkaline to Brilliant Yellow indicator paper. The solution is left for some time at a temperature of about plus 5 C. After a few hours the diazo reaction ceases to be positive (testing with R salt indicator paper),-due to formation of the diazoimino compound of the following probable constitution:

, I ISOaNa on; 01 SOaNa Part B A solution of 330 parts of the sodium salt of 2,3-hydroxynaphthoic-ortho-phenetidide in 1000 parts diethylene glycol and 500 parts water are added to the mixture and the Whole solution is then 1 left ,standing overnight, filtered from possibleuprecipitated inorganic salts and standardized so as to represent 5000 parts total of the dyeintermediate solution. to 400 parts of this solution are then thickened directly with 900 to 600 parts of a neutral starch tragacanth printing paste to proper consistency and applied in acetate.

-. neutralization,

the usual manner on acotton fabric by means of a printing roll. The printed fabric is then dried and subjected to the action of live steam containing acetic acid vapors, which cause the diazoimino compound to hydrolyze very readily into the active coupling 2,5-dichlorobenzene diazonium salt and causes formation on the fiber of, a very brilliant scarlet azo dyestufi of the following probable constitution:

OH OCaHs The printed material is aftertreated according to usual methods.

In a similar manner diazoamino compounds may be prepared fromthe other chlor and nitro substituted anilines aforementioned and the methylamino benzene--oxy-benzyl-W,5- disulfonic acid or alkali salts thereof. The products thus formed are white to yellowish to deeply orange colored powders, readily soluble in water.

They are stable towards alkalies but are decomposed into the corresponding diazonium salts and the free stabilizer, methylamino-benzene-4=-oxybenzyl-2',5'-disodium disulfonate by the action of :acid reagents thereon.

EXAMPLE 4 932 parts of a bis-diazoamino compound obtained from two molecular equivalentsof 2-nitro- 4-methyl-phenyl-diazonium chloride and about 1 molecular equivalent of 3,3'-di(ethy1amino) -d.iphenylmethane-G,6di(oxy disodium succinate) (amine #38) having the probable formula:

CIlaCOONa 02115 0112- 0 ONa imino separates. This product may be filtered oif, washed and dried in any suitable manner.

The above coupling reaction also may be accomplished on textile fibers when proceeding with the mixed solutions of the diazoimino compound and the coupling component ,according to the method illustrated in Example 2.

Emmi? An aqueous solution of'the diazoimino compound formed by coupling 2-nitro-14-methoxy phenyl-diazonium chloride and l methylamino benzene-. l-oxy-sodium" acetate (amine #41) of the following formula:

HaC-OQNflViITO-O-C 111-0 0 ONa is treated with an alkaline aqueous aceto-acetyltoluidide solution containingequimolecular quantitles of the aceto-acetyl-toluidide, in the manner set forth'in Example 4. An orange yellow azo,

dye of; theprobable formula:

Lo fing is thusobtained.

' EXAMPLE 6 To-1000 parts by weight of an aqueous sumtion containing'w parts by weight of--the-diazo'-- imino compoundobtained from 2-methy1-5- chlorphenyl diazonium. chloride and l-methylamino-benzene-4-oxy-phenyl-4'-oxy sodium acetate-5-sodium sulfonatei (amine #32), and having the probable formula:

Cl SOaNa there are added parts acetictacid, 5 parts of alum and 5 parts of sodium acetate.

Cotton fabric is impregnated in the customary manner with the sodium salt of 2-hydroxy-3- naphthoic.acid-Zflnaphthylamide; for instance, grams. of cotton may beimpregnated with. a t

liquor containing to 5 grams of the amide,

about 1 to about 10 cos. of 34 B. (28%) NaOH,

and about 1 to about 10 cos. Turkey red oil of 50% strength.

Theimpregnated cotton is introduced into the;

bathcontaining the acidified diazoimino compoundand the bath is slowly heated to about 50 to C. The formation of the az'o dyestuif on the fiber occurs very, readily. I It has the probable formula:

64 CH3 HO When the-diazo compound can no longer be detected in the .pbath, the cotton is removed therefrom, is rinsed, soaped at boiling temperature, rinsed again; and dried. A brilliant red of excellent fastness is thus obtained.

azoniumf' chloride and the sodium salt of 1-methylamino-3-chlorbenzene 6 oxy phenyl- I m'onosulfonic acid (amine #30), and having the 5 O :Na

in -slightly alkaline solution, is mixed in equimolecular ratio with 2-hydroxy-3-napht'hoic acid-2'-anisidide in an aqueous solution containing equimolecular quantities of NaOH. The mixture is evaporated to dryness at low temperature in vacuum.

79 parts by weight of the dry product are made up to 1000 parts with 50 parts Turkey red oil, 50 parts urea, 600 parts tragacanth thickener, 'and the remainder water. The resultant printing paste may be printed on a textile fiber in usual manner. The printed fabric is passed through the acid vapor ager at a temperature .of IOU-102 C., the ager being supplied with steam containing between .05% and 1% acetic and-05% and /g% of-formic acid vapors to form the azo dye having the probable formula:-

After a short period of contact of the printed fabric with the acid vapors in the ager, say 2 minutes, the material is rinsed, soaped, rinsed and dried. A very brilliant scarlet print is thus EXAMPLE 8 A paste made in the same manner as in Example 7 but containing the diazoimino compound from 2,5-dich1orphenyl diazonium chloride and the sodium salt of 1-methylamino-3-chlorbenzene 6 oxy-phenyl-monosulfonic acid together with 2-hydroxy-3-naphthoic acid-2',5'- dimethoxy anilide as a coupling component instead of the diazoimino compound and coupling component of the previous example, yields a fast brown azo print on cotton, the azo compound having the probable 'formula:

I QN=N 0 CH:

| 01 no com;-

EXdMPLE 9 About 43 parts of the diazoimino compound from 3-chlor-pheny1 diazonium chloride and pmethylamino-phenoxypenta hydroxy {hexane (amine #16) Ha HHHOH and about 28 parts of 2-hydroxy-3-naphthoic acid-2-toluidide were made up to a paste with hot water with the addition of 60 parts of the monoethyl ether of-glycol. To this paste, 30 parts by weight of 36 B. (30%) NaOH, 600 parts by weight of neutral starch .tragacanth thickener were added, and the product is made up to 1000 parts by weight with water. This printing paste is applied to cotton fabric in the usual manner. The print is then steamed for around minutes (or as an alternative is hung in contact with the atmosphere for about 21 hours). The cotton is then introduced for a short time into an aqueous bath, maintained at about 80 to 95 C., and containing 50 grams acetic acid and 50 grams sodium sulfate per liter. By'this treatment the azo dye of the probable formula:

no N110 is developed on the fiber yielding a print of a very brilliant orange shade of excellent fastness. A similar result is obtained by developing the print in an acid bath containing formic, oxalic or another strong organic acid instead of the acetic acid mixture.

Likewise developments in a vapor ager containing a volatile acid such as acetic acid produce similar results.

EXAMPL 10 ceases to couple after a while (this is detectable by a negative test with alkaline R salt solution). Upon adding sodium chloride to the solution a precipitate forms which is filtered off and dried in vacuum. The dried product has a pale brown color, is highly soluble in water, and has the following probable formula:

N-C 2H;

O-QHa-CHOH-CHr-OBOaNa About parts of the above bis-diazoimino compound and 55 parts of 2-hydroxy-3-naphthoic acid aniiide were made up to a paste with 175 parts by Weight of Water and the addition of Thereafter the print was rinsed, soaped at boil,

rinsed, and finished in the usual way.

It will be obvious from the above examples that the procedure involved in the preparation and use of these new diazoimino compounds or compositions is capable of almost limitless variations. Any of the usual methods of developing azo dyestuffs by coupling diazoimino compounds 7 and coupling components may be employed with the diazoimino compounds of the present invention.

The following table further illustrates the nature of compositions of dyes that may be obtained by the application of my invention. In this table shown the shades of dyeings obtainable with the diazoiniino compounds and the coupling components set forth. It will be understood that such dyeings may be obtained by substantive preparation, or by printing textile fibers with a printing paste containing the diazoimino compound and the coupling component and subsequently developing, or by impregnating the textile fiber with one of the components and subsequently developing the dye by bringing the impregnated fiber into contact with the other component under conditions favoring azo coupling.

N 0. Base No. Stabilizer Coupling component Shade 1 2.5-dichlor-l-aminobcnzcne 4 l-mc hyl-3-ami o-benzene-4-0xy- Diacetoacctyl-o-tolidide n ethyl-sulfonic acid. 2 do 11 1methyhmino-benzene-Z4-di(oxy- 2,5-dichlor-4-nitro-1-aceto-acety1 D acetic acid). amino-benzene. 3 4-chloro-2-amino-1i'nethyl-benzene. 18 l-ethylaminc-Inetliylbenzcne-2,4- Diacetoacetyl-o-tolidide D dl-(OXy-GtbyLSllllOnlB acid). 4 4,5-dichlor-2-amino-l-methylben- 29 -cthylamino3-chlorbcnzene-fi-oxydo zene. malonic acid. 5 l-chloro-2-amino1'mctli0xy-ben- 36 1,4-di-(paramctliylamino-jocncyl- .do D

zone. oX.y)-benzene-disuifonic acid. 6 2,5-dichloro-l-methyli-amino- 2 6 l-methylamino-naphthalene-ido D benzene. oxy-acetic acid. 7 5-nitro-2-amino-1-methylbenzone. l5 l-methylammobcnzene-2,4-di-(oxy- Sodium compound of 4-nitro-2,5-di- D ethyl-snifonic acid). niethoxy-l-aceto-acetanilide. 8 S-chloro-l-aminobcnzene 32 l-methylaminobenzenei-oxyphe- 2-liydroxy-naphthalene-3-carbox- Orange.

nyld-oxy-acetic-5-su1fonic acid. ylic-o-toluidide. 9 do 7 l-methyiaminobenzene-2,4-di-(oxy' Sodium compound of 2-hydroxy- D ethyl-sulfuric acid). iiiaghthalene-3-carboxy1ic-o-tolui- D 1 e. 10 2,5-dichloro-1-aminobenzene 20 Ethy]aminobenzonc-para-oxy-(2- 2-hydrqxy-naplithalenei-carboxylic- DQ hydroxy)propyl-snlfuric a d. acid-o-phenetididc. 11 do 5 l-methy]-3 methylaminobenzene-4- Sodium compound of z-hydroxy- D OXYGthyI-SUKUIIO acid. naphthalcne-3-carboxylic acid-ophenctidide. 12 4-chlor-2-amino-1-methyl-bonzone. 23 l-methylaniino-na hthalene-2-oxy- 2-hydroxy-naphthaleno-S-carboxylic s -mt ethyl-sulionicaci acid-o-phenetidide. 13 Z'aminQ- i-methoxy-5-benzoylami- 38 3-3-di(ethylamino)-d plienyl-me- 2-hydroxy-naphthalene-3-carbox- Viol t.

no-l-chloi'obenzene. thane-6,( i-d1(oxy'succinic acid). ylic acid-o-tolnidide. 14 2,fi-dichloro-l-aminobenzene...; 13 l-ethylaminobenzene-i-oxy-methyl- 2-hydr0xy-naphthalene-3-carboxs m.

benzene-2,5-disulionic acid. ylic acid-o-anisidide. 15 do 35 D1- (metl y1amino-phenoxy)-suc- Sodium compound of Z-hydroxy- D cinic 801d naphthalene-3-carboxylic acid-oanisidide. 16 3-chloro-1-aminobenzene 30 l-methylamino-3-chlorbenzene-doxy- Z-hydroxy-naphthalene-3-carboxylic R phenyl-mono-sulfonic acid. acid-o-anisidide. 17 4,6-dichloro-2-amino-l-methyl- 19 1-cyclohexyl-aminobenzene-ZA-di- 2-11ydroxy-naphthalene-Bcarboxylic D benzene. (oxy-methylbenzene-2,5-di-sulacid p-anisidide.

ionic acid) 18 do 25 l-methyiamino-naphthalene-2-oxy- Sodiumcompoundof2-hydroxy-naph- D succinic acid. til iglenod-carboxylic acid-o-anisil e. 19 4-0h10r0-2-amino-1-methyl-benzone 33 1-methylamino-methyl;3-chlor-ben- -...do zene-4-oxysuccin1c acid. 20 4-ch1oro-2-amino-1-methoxy-ben- 6 l-amino-i-hydroxyethoxy-benzenedo D zone. 2-oxy-ethyl-suliuric acid. 21 4-0111oro-2-amino-l-methy1-bonzone 17 1-ethylaminomethylbenzenc-fl, i-di- Z-hydroxy-naphthaleno-3'carboxylic- D (oxy-aceticamd). acid-o-toluidide. 22 do 8 l-methylamino-benzene-i-glyceryl- Sodium compound of 2-hydroxy- D phosphoric acid. na i l(11tl1alene-3-carboxylicacid anii e. 23 4-amino-1,3-dimethylbenzene... 21 l-methylamino-3-chlorbenzene-6- 2-hydroxy-naphthalene-3-carboxylic Turkey red.

\ oxy-acetic acid. acid-2'-methyl-i-mcthoxy anilide. 24 l-niti'o-2-amino-1methoxybenzene 10 l-mcthylamino-inethy1benzene-4- Sodium salt of 2-hydroxy-naphtha- Bluish red.

' oxy-ethyl'sulionic acid. leged-carboxylic acid-m-nitro-anil e. 25 4,5-dichloro-2-amino-1-methylben- 16 l-inethylamino-benzenc-4-oxy-pen- Sodium compound 'of 2 -hydroxy- Turkeyrcd.

zene. tahydroxy-hexane. naphthalene-S-carboxyhc acid-mnitro-aniiidc. 26 .do 40 3,3 di(ethylam1no) 6,6 di(2,5 2-hydroxy-naphthalene-3-carboxyiic D disulfobenzyloxy) dipheny1 acid-p-anisididc. methane. 27 E-nitio-2-amino-1-methylbenzene 34 l-methlamino-bcnzenei beta-oxy- Sodium compound of 2-hydroxy- Bordeaux.

naphthalene-sulfonic acid. naphthalene-3-carboxylic acid- Q o-toluidide. 28 do 33 1-methylammo-mcthykB-chlor-ben- 2-hydroxy'naplithalcne-3-carboxylic D ZBDB-i-OXY-SUCOIDIO acid. e

acid-o-tolmdid No. Base No. Stabilizer Coupling component Shade 29 -nitro-2-amino-l-methoxybenzene. 22 l-methylamino-3-chlorbenzenc-G- Sodium compound of Z-hydroxy- Do.

oxy-succinic acid. naphthalene-3-carboxylic acid alpha-naphthyl-amide. 30 3-amino-4- met oxy 6 nitro 1 12 1-methylamino-benzene-4-oxy-me- 2-hydroxy-naphthalene- 3 carbox- Do.

mcthylbenzenc. thylbenzene-2,5-disu1fonic acid. ylic acid-alpha-naphthylamide. 31 .do 9 l-methylamino-methylbenzcne-Z- Sodium compound of Q-hydroxy- Do.

oxy-acetic acid. naphthalene-3-carboxylic acidalpha-naphthyl-amide. 32 .do 14 l-aminobenzene-4-oxy-ethyl-sulfonic 2-hydroxy-naphthalene-3-carboxylic Do.

aci acid-beta-naphthyl-amide. 33 ..do 24 1-methy1amino-naphthalene-2-oxy 2-hydroxy-naphthalene-3-carboxylic Do.

acetic acid. acid-2,5-di-methoxy-anilide. 34 5-nitro-2-amino-1-methoxybenzene. 31 l-ethylamino-3-ch1orbenzene-6-oxy- Sodium compound of 2-hydroxy-3- Do.

phenyl-di-sulfonic acid. cargoxylic acid-alphanaphthylam1 e. 35 3 -amino -4-methoxy-6-benzoyl- 21 1-methylamino-3-chlorbenzene-6- Sodium compound of 2,3-hydroxy- Violet.

amino-l-methylbenzene. oxy-acetic acid. naphthanilide. 36 do 28 1-ethy1amino-naphthalene-4oxy- Sodium compound of 2-hydroxy- Do.

succinic acid. naphtha1ene-3-carboxylic acid-otoluidide. 37 do 27 l-methylamino-naphthalene-4-oxy- Z-hydroxy-naphthalene-3-carboxyhc Do.

ethyl-sulfonic acid. acid-o-toluidide. 38 6-amllSl0-4-benz0y1afl1lll0-1,3-d1'- 39 3,3-di(othylamino)-6,6-di(sulfonyl- Sodium compound of 2,3-hydroxy- Do.

methoxybenzene. phenoxy)-diphenyl-methane. naphthanilide. 39 do 35 Di-(methylamino-phenoxy)-succinic Z-hydroxy-naphthalene-3-carboxyhc Do.

ac acid-o-toluid e. 40 .....do 9 l-methylamino-methylbenzene-2- Sodium compound of 2 -hyd roxy- Do.

. oxy-acetic acid. naphthalene-3-carboxyl1c acid-5- chlor-2-t0luidide. 41 4,4-diamino-3,3-dimethoxy-azo- 37 3,3 di(methylamino) diphenyl 2-hydroxy-naphthalene-3-carboxyhc Blue. benzene. mcthanedfi dfloxy-acetic acid). acid-o-toluidide. 42 6 amino 3 benzoylammo 1 4 6 1-an.1i.no-4-hydroXy-ethoxybenzene- Sodium compound of 2 hydroxy- Do.

' diethoxybenzene. 2-oxy-ethyl-sulfuric acid. palphghilene-ii-carboxyhc acid-oo m 1 e. 43 do 21 l-methylamino-3-chlorbenzene-6- 2,3-hydroXy-naphthani1ide---. Do.

oxy-acetic acid. 44 6-amino-3-benzoylam1no=4-ethoxy- 13 l-ethylamino-benzene-4-oxy methyl- Sod1um compound of 2-hydrogry- Do.

l-methoxybenzene. benzene-2",5-disulfonic acid. naphthalene 3 carboxylic acid v ortho-toluidide. 45 .do 22 1-methylamino-3-chlorbenzene-6- Sodium salt of 2,3-hydroxy-naphth- Do.

oxy-succinic acid. anilide. 46 6-amino-3-benzoy1amino- 1,4-dil-methylamino-metbylbenzene-4- Sodium compound of 2-hydrogcy- Do.

methoxy-benzene. oxy-ethylasulfonic acid. naphthalene 3 carboxylic acid ortho-toluidide. 47 ..do 9 1-methylamino-methylbenzene-2- d D0.

. oxy-acetic acid. 48 4-chlor-2-amino-l-methyl-benzene. 14 l-aminobenzcne-i-oxy-ethyl-siflfonic Sodium compound OfZ-hYdI'QXY-Oar- Brown.

acid. bazole-ortho -carboxylic acid-2- toluidido. 49 4-nitro-4-ammo-2,5-dimethoxy- 2A 1-methyla1nino-naphthalene-2-oxy- Sodium compound of Z-hydroxy- Black.

azobenzene. acetic acid. naphthalene 3 carboxylic acid v ortho-toluidide. 50 3-nitro-4-amino-2,5-dimethoxy- 37 3,3 di(methylamino) diphenyl Sodium compound of Z-hydroxy- Do.

azobenzene. methane-6,6-di(oxy-acetic acid). naphthalene-3-carboxyl1c acidalpha-naphthylamide. 51 4-methyl-4-amino-2-methoxy-5- 29 l-ethylamino-3-chl0rbenzene-6-oxy- Sodium compound of Z-hydroxy- Do.

methylazo-benzene. malonic acid. naphthalene-3 -carboxyl1c acid ortho-toluidide. 52 4-chlor-4-amino-2',5-diethoxy-azo- 33 l-methylamino-methyl-3-chlor-ben- Sodium compound of 2-hydrogry Do.

benzene. zene-4-0xy succinic acid. naphthalene 3 carboxyhc acid alpha-naphthylamide. 53 4-nitro2-amino-1-methoxy-benzene. 42 l-methyl-3-methy1amino-benzene-4- Sodium compound of 2-hyd roxy- Bluish red.

oxyethyl-sulfmic acid. naphthalene-3-carboxyhc acid-mnitro-anilide. 54 5-nitro-2-amino-to1uene 43 2-ethylamino-4-chlorphenoxy-butyl- 2,3-hydroxy-naphthoic-ortho-tolu1- Bordeaux.

sulfuric acid. dide. 55 do 43 2-ethylamino-4-chlorphenoxy-butyl- Sodium compound oi 2, 3-hydroxy- Do.

sulfuric acid. naphthoic-ortho-tolindide.

I claim: 4. As a new compound a symmetrical aromatic 1. As a new compound an aromatic diazoamino ether comprising on one side of the diazoamino group an aromatic group joined directly to the diazo group, which aromatic group is capable of forming with an azo coupling component an insoluble azo compound, and on the other side a solubilizing group separated fromthe diazoamino group by an ether oxygen atom.

2. As a new compound an aromatic diazoamino ether comprising on one side of the diazoamino group an aromatic group joined directly to thediazo group, which aromatic group is capable of forming with an azo coupling component an. insoluble azo compound, and on the other side a water-solubilizing partial ester group separated from the diazoamino group by an ether oxygen atom.

3. As a new compound an aromatic bis-diazoamino ether comprising on the one side of each of the two diazoamino groups an aromatic group joined directly to the diazo group, which aromatic group is capable of forming with an azo coupling component an insoluble azo compound, and on the other side a solubilizing group separated from the diazoamino groups by an ether oxygen atom.

bis-diazoamino ether comprising a pair of twin aromatic diazoamino ether radicals comprising on the one side of the diazoamino group an aromatic group joined directly to the diazo group, which aromatic group is capable of forming with an azo coupling component an insoluble azo compound, and on the other side a solubilizing group separated from the diazoamino group by an ether I oxygen atom, said radicals being joined to one another by a carbon-to-carbon linkage to form a symmetrical molecule. i

5. The method of producing an aromatic diazoamino ether of the type set forth in claim 1,

which comprises coupling the diazonium salt of an insoluble aromatic amine with an amino ether having a solubilizing group separated from the amino group by an ether oxygen atom. 6. The method of producing an aromatic diazoamino ether of the type set forth in claim 2, which comprises coupling the diazonium salt of an insoluble aromatic amine with an amino other I having a water-solubilizing partial ester group separated from the amino group by an ether oxygen atom.

" '7. The method of producing an aromatic bis- 75 diazoamino ether of the type set forth in claim 3, which comprises coupling two 111915 of the diazonium salt of an insoluble aromatic amine with one mol of a, diamino ether havinga. solubilizing group separated from the amino group by an ether oxygen atom.

i 8. Themethod of producinga symmetrical aromatic bis-diazoamino ether of the typeset forth in claim 4, which comprises coupling two mols of the diazonium salt of an insoluble aroinatio arnine with one mol of a diamino ether comprisinga pair of twin amino ether radicals containing a. solubilizing group separated from the amino group by an ether oxygen atom, said radicals being i joined to one another-by a oarbon-to-carbon linkage to form a symmetricalmolecule.

JEAN G. KERN.

CERTIFICATE OF C ORREC TI ON.

Patent No 2, 190 8M1 February 20 1 911,0

JEAN G. KERN.

It is hereby certified that error-appears in the printed specification of the above numbered patent requiring correction as follows: Page 5, first column, line 56, formulae 5, for "aicd" read acid; page 1 first column, line L5, formulae 2?, for "9-methylamino" read l-methylamino; page 8, second column, line 1h, for "acid-Z-toluidide" read acid-21-toluidide; page 9, line 55-56, in the table, second column thereof, for "(oxy-methylbenzene-2,5 -di-sulfonic acid)" read (oxymethylbenzene2v,51-di-sulfonic acid); line 72, same column of same table, for "l-rnethlamino" read l-methylamino; page 10, line 19, in the table, second column thereof, for "-6,6" read 6,6'; page 11, first column, line 5, claim 7, for "group"'read groups; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 16th day of April, A. D. 19m

Leslie Frazer (Seal) Acting Commissioner of Patents 

